CN102869425B

CN102869425B - Steam suppressant additive

Info

Publication number: CN102869425B
Application number: CN201180009720.9A
Authority: CN
Inventors: 菲尔·杰克森; 莫塔兹·伊布拉伊姆·阿塔拉; 本杰明·杰克·巴林杰
Original assignee: Commonwealth Scientific and Industrial Research Organization CSIRO
Current assignee: Commonwealth Scientific and Industrial Research Organization CSIRO
Priority date: 2010-02-19
Filing date: 2011-02-21
Publication date: 2016-05-11
Anticipated expiration: 2031-02-21
Also published as: EP2536482A4; AU2011202257B2; WO2011100806A1; US8609049B2; CA2788978A1; JP5854519B2; US20130052110A1; JP2013519514A; CN102869425A; EP2536482A1; AU2011202257A1; KR20130000393A

Abstract

Disclosed a kind of for from containing CO at this₂Gas flow in remove CO₂Method, wherein should contain CO₂Gas flow contact with a kind of water-based ammonium salt solution. This water-based ammonium salt solution comprises that the ammonia of 0.1%-40%w/v, v/v/w/w and a kind of concentration range are the soluble salt of 0.01%-10%wt or v/v or w/v, the cation that this soluble salt has is the group that is selected from IA, IIA, IIIA and IVA family metal, is anion, the NO that is selected from VIIA family element together with counter anion₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-And HCO₃ ^-Group. The present invention also expands to a kind of CO that comprises water-based ammonium salt solution and above soluble salt₂Trapping solvent.

Description

Steam suppressant additive

Invention field

The present invention relates to amine and their purposes in capturing carbon dioxide from air-flow.

Background of invention

Exist ever-increasing pressure for the fixing producer of greenhouse gases and significantly reduce their airborne release.Special concern be carbon dioxide (CO₂) to the discharge in atmosphere. Reduce Atmospheric CO₂A kind of method of discharge is by onePoint source by its trapping and be stored in subsequently geology or other holders in.

For from power station and the device of other combustion product gases trap CO₂Method be called as burning after trapping(PCC). The most ripe commercially available technology for PCC is the CO based on solvent₂Absorb/discharge. When the extensively PCC skill of popularization of practiceWhen art, will require a large amount of solvents, as ammonia and amine. From another perspective, the typical case of the black coal of a burning pulverizing2.4GW generator has produced about 30-50 ton CO₂/ minute, or 680kmol/ minute. Be clear that, by the PCC in this gradeThe quantity of solvent recycling in factory is unprecedented. Diving of solvent and degrading solvent product (producing by oxidation and thermal process)Need to consider at ambient influnence, especially when being discharged in local environment with this scale by solvent slippage (slippage)When Shi Keneng is inevitable.

For CO₂The most attractive physical solvent of trapping is to have those of following characteristic, such as: high heat stabilityProperty, extremely low steam pressure, incombustibility and nontoxicity. This type of material has with solvent loss minimum in gas flowTrap CO₂Potentiality.

Use ammonia solution from smoke gas flow, to remove CO₂Attractive from chemical viewpoint, have with respect to fromIn admixture of gas, reclaim CO₂Permanent known use monoethanolamine (MEA) or other amine as solvent system manyIndividual important advantage. These advantages comprise:

1.SO_xAnd NO_xCan be absorbed, its possibility is by spent solvent solution as fertilizer sources (SO_xAnd NO_xDegradedAmine solvent) and advantageously sell.

2. in business application widely, ammonia is one chemicals cheaply.

3. be for MEA system desired approximately 40% for this kind of desired gross energy design of method.

About this ammonia process, this solvent solution is by ammonium, bicarbonate ion and the carbonate group to a less degreeBecome the ammonia (water-based) of this carbonate and dissolving and the CO dissolving₂(water-based) balances each other. In this absorption tower, water and ammonia and CO₂(water-based) reacts to form bicarbonate ion or carbamic acid ammonium ion, and wherein this reaction is passed through in stripperApply energy and inversion occurs. These aqueous phase reactions that are associated can be summarized by following overall equation:

(equation 1)

(equation 2)

(equation 3)

(equation 4)

Ammonia is a kind of lighter molecules (molecular weight=17 dalton), and it is in the temperature higher than-30 degrees Celsius (in atmospheric temperature)Be more than gas, and be easily dissolved in water. By water-based gas flow (as in a kind of after-combustion trapping process) for ammonium salt solutionBubbling will cause ammonia leave this solution and enter into gas phase. The value that leaves the gas phase free ammonia on this absorption tower is and waterThe value of property ammonia is proportional, and this controls by solution chemistry effect and Thermodynamics (as temperature): higher temperature makesThe value that obtains vapor phase ammonia increases.

It has been the ammonia loss (or " slippage ") being associated with this absorption tower and stripper to the main concern of ammonia process. Be used forA kind of possible approach of alleviating the ammonia slippage from catching apparatus is to use additive to improve the boiling temperature of ammoniacal liquor, thereforeBy salt-or azeotropic be used for reducing ammonia loss.

An object of the present invention is to overcome or at least alleviate and use ammonia as CO₂These of trapping solvent phase associationOne or more in problem.

In this description, mention any prior art not by and should not be considered to that one is admitted or any shapeThe suggestion of formula, that is: the prior art has formed of public general knowledge in Australia or any other jurisdiction of courts regionPoint, or the prior art can be determined, understand by those skilled in the art's rational expectation and be considered as phaseClose.

Summary of the invention

Therefore, in one aspect, the invention provides a kind of for from containing CO₂Gas flow in remove CO₂Method, bagDraw together following steps:

Make this containing CO₂Gas flow and a kind of CO₂The contact of trapping solvent phase; CO₂Trapping solvent comprises or consists of a kind of waterProperty ammonium salt solution and a kind of soluble salt; This water-based ammonium salt solution arrives the ammonia of 40%wt and the concentration range of this soluble salt containing 0.1%wtBe 0.01%-10%wt, this soluble salt has one or more cations that is selected from lower group, and this group is made up of the following: IA,The cation of IIA, IIIA and IVA family metal, is selected from the counter anion of lower group together with one or more, and this group is by followingItem composition: the anion of VIIA element and NO₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-, and HCO₃ ^-And the contending with of other water solublesAnion; And

By CO₂Should be containing CO₂Gas flow in absorb this CO₂In trapping solvent.

In another aspect of this invention, provide a kind of CO₂Trapping solvent, this solvent comprises or is configured to:

The ammonia concentration having is 0.1%wt until a water-based ammonium salt solution of 40%,

And a kind of concentration range is the soluble salt of 0.01%wt-10%wt, this soluble salt has one or more and is selected from downThe cation of group, this group is made up of the following: IA, IIA, IIIA and IVA family metal, be selected from down together with one or moreThe counter anion of group, this group is made up of the following: the anion of VIIA element and NO₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-, withAnd HCO₃ ^-Or the counter anion of other water solubles.

In a preferred form aspect more than of the present invention, the cation of this soluble salt is the one being selected from lower groupOr the cation of multiple element, this group is made up of the following: Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, andThese anion are one or more anion that are selected from lower group, and this group is made up of the following: element F, Cl, Br, I, AtAnion, and NO₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-, and HCO₃ ^-Or the counter anion of other water solubles.

This additive can be that a kind of multiphase solid of a kind of solution of multiple salt, a kind of pure solid or several salt mixesA kind of mixture of thing or multiple aqueous salt (being dissolved in the salt in water). This additive add time can be crystallization, powderShape, melting or any other state. This salt can also add as a kind of crystalline hydrate solid, that is, this salt is onePlant the solid containing the crystallization water. These salt can also add as a kind of solid salt of mixing, for example Na_(X)K(_1-X)Cl. TheseSalt can be dissolved in a kind of and the miscible solvent of water for adding a large amount of water-based ammonium salt solutions to. Of the present invention preferredIn form, the concentration that these water soluble salt are added is 0.1wt-5%wt and is most preferably 1wt-3%wt.

For CO₂The scope of the concentration of the water-based ammonium salt solution of trapping is in the concentration up to 40%wt from 0.1%wt. ThisThe sole purpose of additive is to reduce the value of the ammonia dissolving, the CO comprising in the flue gas of absorption power station₂Time this dissolving ammoniaBe transferred in gas phase. This ammonia can be unique CO₂Trapping solvent or it can blend together with other solvents. These itsHe can comprise any CO by solvent₂Trapping amine, it is in being less than any solubility of the concentration of ammonia in this blend solvent. Some are normalThe chemical constitution of the applicable trapping solvent of seeing is presenting below:

Specifically, this other solvent is to be selected from lower group, and this group is made up of the following: MEA(monoethanolamine), DEA(diethanol amine), AMP(2-amino-2-methyl propyl alcohol), MDEA(methyl diethanolamine) and PZ(piperazine), methyl diethanolamine(MDEA), diglycolamine (DGA) and two-isopropanolamine (DIPA) and two or more blend in them. ThisThe concentration of a little other solvents in this blend solvent is to be less than the concentration of ammonia in this blend solvent. Therefore, therein canUse in a kind of situation of blend solvent, the concentration of ammonia in this solvent is in the scope of 20%wt-40%wt.

In the preferred form of salt of the present invention, this cation is to select in the cation of group of free barium, caesium or rubidium compositionOne or more that select, and this anion is chlorion, PO₄ ^3-Or nitrate anion.

As used in this, unless the place requiring in addition at context, term " comprises " (comprise) and this artThe variation of language, for example " comprise " (" comprising "), " comprising " (comprises) and " comprising " (" comprised ") noBe intended to get rid of other additives, composition, entirety or step.

Brief Description Of Drawings

Fig. 1 is headspace equalizing pressure on the 150ml solution containing 10%wt water-based ammonia and different additiveFigure.

The detailed description of embodiment

Ladies and gentlemen inventor's object is to find a kind of additive, and it will improve the boiling temperature of solution in the time joining in ammoniaAnd therefore reduce NH3 loss by binary azeotropic effect. In this work, to model system CH₃COOH-NH₃(a kind of heat-staple salt), MEA-NH₃, three (THAM)-NH₃、Na⁺-NH₃And HCO₃ ^--NH₃Calculate.

Computational methods

B3LYP/6-31++G (d, p) is fine for relative HYDROGEN BOND INTENSITY effect, and the heat chemistry value producing normallyWithin the 10kJ/mol of result of the test, and it has been used in this example. Use this Scott/Radom of 0.9806The factor determine to scale zero point energy, and the vibrational entropy of partition function contribution is determined to scale by 1.0015.All structures are the temperature for 298.15K. Na⁺-NH₃Except the calculating of calculating, undertaken by Gauss's 03 program in G3 level,Used in a SGI-Altix multinode DDI system (being positioned at Da Kelan (Docklands), VIC)) on the GAMESS that carries outFor calculating. The result of calculating presents in table 1 (a) and 1 (b)

Number in table 1 (a) and 1 (b) can be used for calculating the energy of following reaction:

X-NH₃→X+NH₃

These numerals are presented in table 2.

Static hydrogen bond/the NH of table 2. under 298.15K₃Reaction energy

And then these values can be come for calculated equilibrium constant with following formula,

G＝-RT.ln(Keq).

These values are included in table 3

Table 3. is for the hydrogen-bonded complex compound equilibrium constant that calculated so far

As above finding, with the electrostatic bond of sodium, not unexpectedly, be strong gas-phase key, and balance is towards thisAssociation complex even represents finely in solution phase. About CH₃COOH-NH₃Form CH₃COO^-And NH₄ ⁺Gas-phase chargeThe substantial energy of separation requirement (referring to table 2 (a) and 2 (b)), therefore for CH₃COOH-NH₃The large enthalpy separating enters intoIn these products. For CH₃COOH-NH₃The intensity that has of gas phase dipole-dipole interaction be about 40kJ/mol.

Among studied alkanolamine, MEA has formed, as equally strong with trihydroxy methylamino methane and ammonia mutuallyEffect, can be partial to the complexing of ammonia slightly although this equilibrium constant (298K) has shown tris._（0

Be clear that, it is the strongest that sodium cation tends to complexing, and HCO₃ ^-Product (this hydroxyl that tends to dissociateThe hydrogen of base is not acid).

And if if infer that complex compound formation is that preferred this is that institute is anti-in the equilibrium constant in this whole processReflect, it is followed, and higher solvent boiling temperature will be observed together with volatile minimizing.

Based on this information, MEA should just work as tris goodly in the volatility minimizing of ammonia.

Based on this information, concentration range is that the water soluble salt of 0.01%-10%wt suppresses ammonia in solution by being suitable forVolatility. Tend to steam pressure suppress applicable salt comprise have one or more be selected from lower group cationic those,This group is made up of the following: IA, IIA, IIIA and IVA family metal, together with one or more be selected from lower group contend with cloudy fromSon, this group is made up of the following: the anion of VIIA element and NO₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-, and HCO₃ ^-Or otherThe counter anion of water soluble. These especially comprise that one or more cationic elements that have are to be selected from lower group solvableSalt, this group is made up of the following: the cation of Li, Na, K, Rb, Cs, Fr, Be, Mg, Ca, Sr, Ba, Ra, and these the moon fromSon is to be selected from lower group, and this group is made up of the following: the anion of element F, Cl, Br, I, At, and NO₃ ^-、SO₄ ^2-、OH^-、PO₄ ^3-, and HCO₃ ^-Or the counter anion of other water solubles.

In order to assess the validity of soluble salt in the volatility that suppresses ammonia, carry out following test.

The test procedure of measuring for VLE

For water-based NH₃Solution and steam inhibitor, a kind of interpolation of inhibitor should cause lower headroom flatWeighing apparatus pressure, if suppress to occur (comparing with the equivalent solution of not adding inhibitor).

Steam suppresses %=(P_Unrestraint-P_Suppress）/P_Unrestraint×100

Carried out multiple tests so that assessing the steam of multiple soluble salts suppresses, and these results are presented in Fig. 1,Wherein RunB=BaCI₂; RunC=CsCI; RunR=RbCl; RunA=ammonia and the amino first of RunTHAM=tri-(methylol)Alkane, (HOCH₂)₃CNH₂。

Used in these trials a kind of vapor liquid equilibrium device, it consists of: Parr pressure reactor, some pressuresPower sensor, gas line, thermocouple, control software and water-bath.

This reactor is filled with to the solution of 150ml, this solution by the ammonia of 10%wt and the dissolving salt of 1%wt (as ionSolid adds) composition. Allow this solution temperature balance, simultaneously this system is repeated to exhaust and with nitrogen wash so as fromPurging air in this test sample. Finally, this headroom is found time, and be recorded in more than this liquid pressure (In this headroom) until reach balance (△ p, △ T=0, this Pressure/Temperature remains unchanged and continues at least 1 hour).

These values are carried out to record. Then, under same condition, assess a kind of aqueous solution (when analyzing when the aqueous solution baseLine is proofreaied and correct).

Fig. 1 is headspace equalizing pressure on the 150ml solution containing 10%wt water-based ammonia and different additiveFigure. In the time of these results of seeing in Fig. 1, be worth lowlyer, more tend to suppress NH₃. Any absolute pressure value is all insignificant,Because they are a kind of scopes that have of use is that the transmitter that 0-20 clings to is measured. These relative values are important. ThisThe value of a little y-axles equals the difference between cell pressure reading and actual tests chamber pressure (measuring with barometer).The dividing potential drop of water vapour is 2.3-3.2kPa(0.02-0.03 atmospheric pressure). At room temperature carry out these tests, and reach 70Hour figure (asterisk in the caption of figure) disclosed the effect of laboratory temperature fluctuation to the value of measuring.

Average pressure value=0.153 of a CsCl atmospheric pressure

Correction=the 0.123-0.133 of the dividing potential drop of a water atmospheric pressure (av=0.128 atmospheric pressure)

Average pressure value=0.218 of an ammonia atmospheric pressure

Correction=the 0.188-0.198 of the dividing potential drop of a water atmospheric pressure (av=0.193 atmospheric pressure)

The average steam of CsCl suppresses 34%(scope=29%-38%).

Straight horizontal line under approximately 0.254 atmospheric absolute pressure is to repeat water-based ammonia test (RunC, Run for 3 timesB and RunR) mean value. These results have proved clearly steam inhibitory action of one, and this is due to addition of C=chlorinationCaesium; B=barium chloride, R=rubidium chloride. It is flat that the equalizing pressure obtaining after 5 hours obtains than the 10%wt water-based ammonia that there is no additiveAll flat

Weighing apparatus pressure is lower.

Will be understood that the present invention who discloses in this manual and limit relates to two or more from text or attachedThe all alternative combination of personal feature that figure mentions or apparent. All these various combinations all form of the present inventionSame alternative aspect.

Claims

1. a CO₂Trapping solvent, comprising:

A kind of ammonia concentration having is the water-based ammonia solution of 0.1%wt to 40%wt;

And a kind of based on this CO₂The concentration range of trapping solvent is the water soluble salt of 0.01%wt-10%wt, this water soluble saltThere is the cation of one or more groups of selecting free barium, caesium and rubidium composition and comprise that at least one selects free chloride ion, PO₄ ^3-Counter anion with the group of nitrate ion composition.

2. trapping solvent as claimed in claim 1, wherein, this anion is chlorion.

3. trapping solvent as claimed in claim 1 or 2, wherein, the concentration that these water soluble salt are added is 0.1%wt-5%wt。

4. trapping solvent as claimed in claim 1, wherein, the concentration that these water soluble salt are added is 1%wt-3%wt.

5. trapping solvent as claimed in claim 1, further comprises the solvent that one or more are other, this other solvent choosingFrom lower group: monoethanolamine (MEA), diethanol amine (DEA), 2-amino-2-methyl propyl alcohol (AMP), piperazine (PZ), methyl diethanolAmine (MDEA), diglycolamine (DGA), two-isopropanolamine (DIPA) with and blend, to form a kind of solvent of blend,Wherein the concentration of this other solvent is less than the concentration of the ammonia in the solvent of this blend.

6. one kind for from containing CO₂Gas flow in remove CO₂Method, comprise the following steps:

Make this containing CO₂Gas flow and a kind of CO₂The solution phase contact of trapping solvent; CO₂Trapping solvent comprise water-based ammonia solution andWater soluble salt, this water-based ammonia solution is the ammonia to 40%wt containing 0.1%wt, and the concentration range of this water soluble salt is based on this CO₂CatchThe 0.01%wt-10%wt of collection solvent, the sun that this water soluble salt has one or more groups of selecting free barium, caesium and rubidium composition fromSon selects free chloride ion, PO with one or more₄ ^3-Counter anion with the group of nitrate ion composition; And

By CO₂Contain CO from this₂Gas flow in absorb in this ammonia solution.

7. method as claimed in claim 6, wherein, this anion is chlorion.

8. the method as described in claim 6 or 7, wherein, the concentration that this water soluble salt is added is 0.1%wt-5%wt.

9. method as claimed in claim 6, wherein, the concentration that these water soluble salt are added is 1%wt-3%wt.

10. the method as described in claim 6 or 7, further comprises the solvent that one or more are other, this other solvent choosingFrom lower group: monoethanolamine (MEA), diethanol amine (DEA), 2-amino-2-methyl propyl alcohol (AMP), piperazine (PZ), methyl diethanolAmine (MDEA), diglycolamine (DGA), two-isopropanolamine (DIPA) with and blend, to form a kind of solvent of blend,Wherein the concentration of this other solvent is less than the concentration of the ammonia in the solvent of this blend.